Developing composition for use with photographic materials for the graphic arts

ABSTRACT

The developing composition of the invention has a good storage stability.   A developing composition for use in photographic materials for printing, containing an infectious developing agent, sulfite and a hydrazine compound of the general formula:

United States Patent [1 1 Okutsu et al.

DEVELOPING COMPOSITION FOR USE WITH PI-IOTOGRAPIIIC MATERIALS FOR THE GRAPHIC ARTS [75] Inventors: Eiichi Okutsu; Y'oo Iijima; Haruhiko Iwano, all of Kanagawa, Japan [73] Assignee: Fuji Photo Film Co., Ltd.,

Kanagawa, Japan [22] Filed: Mar. 22, 1972 21 Appl. No.: 237,001

[30] Foreign Application Priority Data Mar. 26, 1971 Japan 46-18123 [52] U.S. Cl 96/66 R, 96/66.3, 96/66.5 [51] Int. Cl G03c 5/30 [58] Field of Search 96/66, 66.3, 66.5, 33

[56] References Cited UNITED STATES PATENTS 2,419,975 5/1947 Trivelli et a1 96/66 R 2,563,785 8/1951 Ives 96/66 R 2,625,475 1/1953 Russell et al 96/66 R 2,835,575 5/1958 Cowden et al. 96/66 R 2,882,152 4/1959 Dickerson... 96/66.3 2,892,715 6/1959 Hunsberger 96/665 1 Feb. 19, 1974 2,962,961 12/1960 Dietz 96/33 3,227,552 l/1966 Whitmore 3,340,058 9/1967 Von Konig 96/28 OTHER PUBLICATIONS Chem Absts. Vol. 57, 1962 .16041d-e.

Primary Examiner-Norman G. Torchin Assistant Examiner-M. F. Kelley Attorney, Agent, or FirmSughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT A developing composition for in photographic materials for printing, containing'an infectious developing agent, sulfite and a hydrazine compound of the general formula: Y

The developing composition of the invention has good storage stability. 1

12 Claims, No Drawings 1 DEVELOPING COMPOSITION FOR USE WITH PHOTOGRAPIIIC MATERIALS FOR THE GRAPHIC ARTS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic developer for developing a high-contrast photographic element useful for the graphic arts.

2. Description of the Prior Art' Photographic linev and halft'one reproductions are carried out by imagewise exposing. a high-contrast or litho-type silver halide photographic element through a cross-screen or contact screen and then developing it with a developer, whereby continuous tone images are converted into photographic line and halftone (dot) images. v

It is most desirable that the line and dot images be composed of only a maximum density portion and a background having a minimum density. However, since a high-contrast photographic element has the property of forming an intermediate density portion besides a maximum density portion and background, a portion of intermediate density which is termed fringe is always formed around the dot images. The formation of fringe is not desirable for graphic arts because it is deteriorates the dot qualities.

As well known in the art, the fringe can be removed by using a so-called infectious developer which essentially contains a dihydroxybenzene type developing agent and a small amount of sulfite ion. In a conventional developer, a dihydroxybenzene type developing agent, for example, hydroquinone is converted into quinone during the developmentprocess and the resulting quinone reacts with sodium sulfite to produce sodium hydroquinone-monosulfonate. However, sodium hydroquinonemonosulfonate is less reductive than hydroquinone due to its low electrode potential, and therefore is almost incapable of acting as a developing agent. Accordingly, the progress of development is not conducted rapidly, thus a fringe is formed. In contrast to this, where an infectious developing agent is used, the concentration of free sulfite ions is maintained at a low concentration, since sodiu'm sulfite is added in a small amount and since it reacts with a compound having carbonyl groups, such as paraformaldehyde, incorporated in theinfectious develop-- ing agent, in accordance with the following equation:

CH O Na,SO H 2 CH ONaI-ISO NaOH For this reason, in the development process it becomes difficult for the quinone to react with sulfurous acid to produce hydroquinonemonosulfonic acid, and thereby the concentration of quinone is increased. The thus produced quinone and the original hydroquinone cause a disproportionation reaction and produce While a sulfite is well known as one of the preservatives for a photographic developer, it is necessary to decrease a concentration of sulfite in order to obtain more effective line and dot reproductions.

Infectious developers of this kind, therefore, have poor stability as compared to common black and white photographic developers, and the life of the infectious developer is short. Consequently, when infectious developers are continuously used, images having a low contrast and a high fringe are obtained because the development is not carried out rapidly. Accordingly, it has been proposed to add an anti-oxidant other than sulfite to improve the stability. In this attempt, it is already known to add ascorbic acid into an infectious developing solution (Great Britain Patent No. 928,390). Ascorbic acid is, however, poor in stability and hence tends to be decomposed. Particularly, ascorbic acid is apt to be decomposed when metal ions such as copper ions or iron ions are present in-a developing solution. Further, it does not sufficiently stabilize the developing solution. Additionally, it has the drawbacks that the progress of development is slowed and that the dot quality is reduced when the ascorbic acid is added in a large amount.

An object of this invention is to provide a photographic developer for a high contrast photographic element useful for the graphic arts having an excellent preservative property unaccompanied by adverse influences on dot qualities.

Another object of the invention is to provide an infectious developer which is easily controlled before and during development.

Still another object of the invention is to provide an infectious developer in which the amount of replenishment during development is reduced.

A further object of the invention to provide a photographic development process for the graphic arts capable of forming line and dot images having good qualities by using an infectious developer stable for a long period of time.

SUMMARY OF THE INVENTION In order to accomplish these objects, various investigations have been made and it has been found that the addition of at least one hydrazine compound represented by the following general formula:

DETAILED DESCRIPTION OF THE INVENTION Suitable examples of compounds which can be used in the present invention are shown as follows. However the invention is not to be interpreted as limited to these compounds.

Compound 1 Number R R2 R3 4 H H n 1r H H H OH: H H H CH3 H CH3 CH3 H H H H y CzHs H H l H C2H5 H OH: H H CzHa OH; H CH3 CH3 CH:

13 ITO: H H H H H H 15 Sameasabove H; H H 16 dO H CH3 H 17 .do G H n 18 CONH: H H H 19 CONHNHz H H H "ffi'eofi ounds are all known compounds and ar e Franklin Inst. (238, 291 (1944)) by A.P.l'l. Trivelli et al. that the development speed is increased when bydrazine is added to a D-8 developer. Further, it has been reported in J. Soc. Sci. Phat. Japan (Vol. 14, 4, 74 (1952)) by M. Tajima that 6-nitrobenzimidazole in a D-8 developer gives some effects to a photographic plate. However, the action of hydrazine in a infectious developer is not yet known.

According to our experiments, it has been surprisingly found that a hydrazine compound improves remarkably the stability of a developer for the graphic arts. The reason a hydrazine compound of the invention improves the stability when added to a developer for graphic arts is not presently understood. But, as will be apparent from the examples described hereinafter, the hydrazine compounds of the invention give rise to an excellent stability and dot qualities in comparison with conventionally known preservatives such as ascorbie acid or excess amounts of sodium sulfite. Particularly, a slowing of the development speed or a formation of a fringe is not observed in the invention.

An infectious developer, in use, is basically composed of a dihydroxybenzene (developing agent), an alkali, a small amount of sulfite and, if necessary, a sulfite ion buffer. The infectious developer of the invention further contains the aforesaid hydrazine compound. I

Dihydroxybenzenes are known in the art and can be easily selected by one skilled in the art. Typical examples of these compounds are hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquionone, toluhydroquinone, 'methylhydroquinone, 2, 3-clichlorohydroquinone, 2,5-dimethylhydroquinone, etc. In developing agents, hydroquinone can be practically used. These developing agentsare used singly or in combination. A suitable amount of the developing generally employed.

4 Egm tobe added rangesfroni 555E615 50g, preferably about 10 to 30g., per one liter of the developer.

A sulfite ion buffer can be used in such an amount that concentration of sulfite is maintained at a low level in the developer. Examples of such buffers are an aldehyde-alkali metal hydrogen sulfite addition product such as formalin-sodium hydrogen sulfite, a ketonealkali metal'hydrogen sulfite addition product such as acetone-sodium hydrogen sulfite addition product, and a carbonylbisulfite-amine condensation product such as sodium bis (2-hydroxyethyl) aminomethane sulfonate. The sulfite ion buffer is not limited to the above examples and each ingredient of the addition product or condensation product may be added to the developer. The amount of the sulfite ion buffer which is added can range from about- 13 to l30g., preferably 30 to 60g. per one liter of the developer.

An alkali is added to adjust the developer to an alkaline condition preferably to a pH higher than 8, more preferably to a pH of 9 to l 1. Accordingly, the addition amount and kind of additive can be freely selected and is not limited to the above examples. The developing solution can contain further a pH buffer agent, such as an alkanolamine, a water-soluble acid (e. g., acetic acid, boric acid), an alkali (e.g., sodium hydroxide) or a salt (e.g., sodium carbonate). Further, it may contain an alkali metal halide as a development controlling agent. Also, it may contain in some cases an organic antifogging agent (e.g., benzotriazole, l-phenyl-S-mercapto-tetrazole), a polyalkylene oxide, an amine, and an organic solvent (e.g., triethylene glycol, dimethylformamide, methanol, cellosolve) in an amount of not more than 300 ml per 1 liter of the developing solution.

As described above, a characteristic of the infectious developing solution is that the concentration of free sulfite is low. For this purpose, a sulfite ion buffer material such as formaldehyde-sodium bisulfite adduct is In general, the concentration of free sulfite ions is controlled by the addition of an alkali metal sulfite such as sodium sulfite in an amount of not more than 5 g per lliter of the developing solution as well as a sulfite ion bufier agent. Sulfite is generally added in an amount of not more than 3 g per liter of the-developing solution, and thereby the stability of the developing solution is slightly improved, although the dot quality is more or less reduced. However, as described above, this degree of the stability is generally not satisfactory. Although ifieaiih iiimis' of the present invention improve the inherently poor stability of an infectious developing solution which does not contain an alkali sulfite other than a sulfite ion buffer agent such as a formaldehydesodium bisulfite adduct to a certain extent, they remarkably improve the stability of an infectious developing solution which contains both an alkali sulfite in an amount of not more than 5 g per 1 liter of the developing solution (0.005-0.05 mole of free sulfite) and a sulfite ion buffer agent.'That is to say, the compounds of the present invention excert an effect even ina developing solution which does not contain a free sulfite (e.g., a developing solution which does not contain a sulfite other than formaldehyde-bisulfite adduct), but this effect is very small. Accordingly, from a practical .standpoint the present invention can be employed best in a developing solution containing a small amount of free sulfite. A single compound of this invention or a combination of two or more compounds of this invention can 5565156;'riieaifiaifiidrifie compounds of the present invention added to a developing solution varies according to the composition of the developing solution and the kind of the compounds used, but the amount employed generally is in the range of from 0.1

g to 20 g per 1 liter of the developing solution, more preferably from 0.5 g to 5 g per 1 liter of the developing solution.

When the developing compounds are processed prior to use so that they may be readily used as developing solutions on mixing with water or dissolving in water, that is, when they are in the form of liquid or powdered developing compositions, it is effective to incorporate the compounds of the present invention into the developing preprationsbeforehand. When liquid preparations are used, it is particularly effective to add the compounds of the present invention since they improve remarkably the stability of the liquid preparations. Liquid preparations generally are not known to have a good stability, and therefore it is difficult to obtain a stable developing agent, since the liquid preparations can not contain a large amount of salts (e.g., carbonylbisulfite) due to the characteristics of liquid preparations. Therefore, it is particularly desirable to use the hydrazine compounds of the present invention in liquid preparations.

A general liquid preparation comprises two liquid compositions, that is, a liquid component containing the developing agent and a liquid component containing an alkali. The compounds of the present invention may be incorporated into any such components, but it is particularly effective to add them to the component containing the developing agent. With this treatment, a liquid developing agent having an excellent stability and an infectious developing solution prepared by dilution of said liquid developing agent having a markedly excellent stability, can be obtained.

As solvents for the liquid developing agent, there may be used solvents such as water, benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, glacial acetic acid or a combination of these solvents. Alternatively, it is possible to improve the stability of the developing solution by'adding the compounds of the present invention in the course of development or.

after development of the photographic materials for printing.

Light-sensitive materials for printing, used in the present invention, include common silver halide emulsions (e.g. silver chloride auisiasgsaver chlorbbro mide emulsions, silver chloroiodobromide emulsions).

. Particularly, silver chlorobromide emulsions and silver chloroiodobromide emulsions, containing not less than about 50 mole of silver chloride, are suitable for the present invention; As silver halide-dispersing agents containing these light-sensitive materials, hydrophilic colloidal substances, such as gelatin or gelatin derivatives (e.g., collodion), hydroxyethylcellulose, carboxymethylcellulose; water-soluble starches (e.g., dextrin, alkali starch); or hydrophilic polymers (e.g., polyvinylalcohols, polyvinylpyrrolidines, polyacrylamides, polystyrenesulfonic acids) can be used. These lightsensitive materials may contain additionally hydrophobic polymers such as polyacrylates, and gelatinplasticizers such as glycerin or trimethanolpropane.

The emulsions used in these light-sensitive materials may be sensitized using various techniques either when the materials are manufactured or when the materials life applied. For example, they may be chemically sensitized by methods well known in the art, for example, with sodium thiosulfate, alkylthiourea, gold compounds such as complexes of monovalent gold and thiocyanic acid, or mixtures of these. Further, the emulsions may contain heavy metals such as platinum, palladium, iridium, rhodium or cadmium. In addition, the emulsions may be panchromatically or orthochromatically sensitized with color-sensitizers such as cyanine dyes or merocyanine dyes. Yet further, the emulsions may contain dot quality-improving agents such as polyalkyleneoxides and amine compounds (U.S. Pat. No. 3,288,612, German Specification OLS 1,932,882, US. Pat. No. 3,345,175), and sodium benzenethiosulfate, benzenetriazole and l,3,3a,7-tetrazaindene derivatives (U.S. Pat. No. 3,375,114 or U.S. Pat. No. 3,333,959). The emulsions may be hardened with formaldehyde, resorcylaldehyde dimethylol urea, 2, 4-dichloro-6- hydroxy-l, 3,5-triazine (U.S. Pat. No. 3,325,287) or mucochloric acid, or they may contain surface-active agents such as saponin in order to facilitate the application of the emulsions. The emulsions may further contain agents which improve the progress of development such as 3-pyrazolidone derivatives or pyrazolone derivatives. Further, the emulsion may contain development-accelerating agents such as quaternary ammonium salts or cationic surface-active agents. The supports used in the present invention are not limited, and glass, cellulose acetate, polystyrene, polycarbonate, polyethylene terephthalate and the like may be used.

The present invention will now be illustrated in greater detail by the following examples.

EXAMPLE 1 Developing Solution A Sodium Carbonate (monohydrate) 50 g Formaldehyde-Sodium Bisulfite Adduct 45 g Potassium Bromide 2 g Hydroquinone 18 g Sodium Sulfite 2 g 1 Water to make 1 liter Developing Solution B Developing Solution B was prepared by adding 1.0 g of Compound-2 described hereinbefore additionally to Developing Solution A.

Developing Solution C Developing Solution C was prepared by adding 3 g of sodium sulfite additionally to Developing Solution A.

Developing Solution D Developing Solution D was prepared by adding 1 g of ascorbic acid additionally to Developing Solution A.

The results obtained are Showniu Table ldescribed in the Japan Patent Publication No.

Table '1 Developing Amount Development Dot Sensitivity Solution Additive Added Time (min.) Quality Fresh Aerated A I 2 Y4 a 100 34 B Compound-2 L 2 3a a 100 95 C Sodium 3.0 3 c 100 65 Sulfite D L-Ascorbic 1.0 3 b 100 60 Acid The development time set forth in Table i above is expressed as the time required to reach the sensitivity obtained when developmentwas conducted for 2 minutes using the Developing Solution A, and this sensitivity is set at 100. The dot quality was graded as a, b and 0, representing good, somewhat good and bad, respectively. The aerated sensitivity was obtained by placing 500 ml of developing solution in a 20 cm X 25 cm developing bath and contacting such with air for 5 hours to determine the deterioration.

As can be seen from the results contained in Table 1, Developing Solution A with no additive shows a great decrease in sensitivity when aerated. Developing Solution C containing 3.0 g of added sodium sulfite shows a smaller decrease in sensitivity than the Developing Solution A does, but is greatly deteriorated and the dot quality of the fresh solution is poor. The hiterto known Developing Solution D containing. 1.0 g of L-ascorbic acid shows almost the same decrease in sensitivity as Developing Solution C when aerated, but this is still unsatisfactory. On the other hand, Developing Solution B containing l.0 g of the Compound-2 of the presentinvention shows the smallest decreases in sensitivity "when aerated, and no decrease in the dot quality was observed at all.

EXAMPLE 2 A lithographic film was prepared was follows. A silver halide emulsion containing 75 mole of silver chloride and 0.2 mole of silver iodide, the remainder of the halide being silver bromide, was subjected to gold sensitization and sulfur sensitization, and then was photosensitized 'with 3-carboxymethyl-5-(2-(3- ethylthiazolinilidene) ethylidene) rhodamine. Then, thereto were added a polyoxyethylene nonylphenylether containing ethyleneoxide groups, the development-accelerating agent Table 2 I Developing V W Amount Development Dot Sensitivity Solution Additive Added(g/l) Time (min.) Quality Fresh Aerated E 2 x a 100 7' 31 F Compound L0 2 Y: a 100 90 C The deveioping solution containing conipoun d-li shows a smaller decrease in sensitivity, in comparison Q with a developing solution which did not contain Como,H, cm pound-3.

23,465/65, mucochloric acid and polybutylmethacrylate. The mixture was then coated on a film base to manufacture the desired lithographic film.

An exposure wedge for sensitometry was'photographed through a ISO-line magenta contact screen, using this lithographic film. The film was then treated at 20C with the two kinds of the developing solutions having the following compositions.

Developing Solution E was prepared by adding Solution l and Solution 2, in this order, to 750 ml of distilled water.

Developing Solution F Developing Solution F was prepared by adding 1.0 g of Compound-3 of the present invention to Solution 1 employed in Developing Solution E, mixing the resulting solution with Solution 2, and making the volume 1 liter.

The results obtained are shown in Table 2.

9 EXAMPLE 3 After photographing an exposure wedge for sensitometry through a ISO-line magenta contact screen, using a commercial lithographic film, development was conducted at 20C, using developing solutions of the following compositions:

Developing Solution G Sodium Carbonate (monohydrate 40 g Formaldehyde-Sodium Bisulfite Adduct 60 g Potassium Bromide 2 g Boric Acid 3 g l-lydroquinone 18 g Sodium Sulfite 2 g Water to make 125 ml The supplementary solution was prepared by adding Solution 1 and Solution 2 to 750 ml of water.

To one of the automatic developing apparatus .was added 25 g of Compound-l of the present invention, and no addition was made to the other. Both apparatus were allowed to stand for 64hours. Then, the lithographic films were developed in each automatic development apparatus. No decrease in sensitivity was observed with the automatic developing apparatus to which the compound of the present invention had been added. On the other hand, a great decrease in sensitivity was observed with the automatic developing apparatus to which no compound of the present invention had been added.

EXAMPLE After photographing an exposure wedge for sensitometry through a ISO-line magentacontanct screen, using a commercial lithographic film, development was .Tflbl9 Developing Additive Amount Development Dot Sensitivity 1 Solution (compound Added Time' min.) Quality Fresh Aerated N (gm 0 2 it a 100 37 H l 1.0 do. a do. 70 l -4 2.0 do. a do. 98 .l- -5 [.0 do. a do. 90 K 6 2.0 do. a do. 85 L 7 1.5 do. a do. 80 M 8 0.5 do. a do. 93 N 9 2.0 do. a do. 93

EXAMPLE ,4

Each of two liter portions of the developing solution used in Example 2 was placed in two developing apparatus for engraving. In each 200 sheets of a half out lithographic film were processed, with the addition conducted at 20 C using developing solutions of the following compositions:

Developing Solution 0 Solution l Distilled Water 70 ml 7 Tiethylene Glycol 30 ml Formaldehyde-Sodium Bisulfite Adduct g Hydroquionone 18 g Triethanolamine 40 ml Sodium Sulfite 2 g of 70 ml of a supplementary solution of the following Distllled Water 10 make 167 ml composition for each sheet of the half-cut lithographlc l 45 solution 2 film.

Distilled Water 120 ml Sodium Carbonate(monohydrate) 30 g Y Sodium Hydroxide 5 g Potassium Bromide 2.5 g Supplementary Sol ion Distilled Water to make 167 ml Solution 1 Distilled Water 30 ml Triethylene Glycol 45 ml Formaldehyde-Sodium Bisulfite Adduct 45 g g ggy q yf 5g 8 Developing Solution 0 was prepared by addlng Solug fg 1; to make 253ml 5 tion 1 and Solution 2 to 666 ml of water to make the volume 1 liter. Solution 2 Developing Solutions P, Q, R, S Distilled Water 90 ml 0 Sodi m cfl n t ydrate) 30 3 These were prepared by adding Compounds-l l, -l 3, gg g 'z' g g 'gfifi a: -l5 and -l8, respectively, to Developing Solution 0. Distilled water to make I25 ml The results obtained are shown in Table 4.

Table 4 Developing Additives Amount Developing Dot Sensitivity Solution (Compound No.) Added(g/l) Time (min.) Quallty Fresh Aerated o 2 at a 100 45 P l l 1.0 do. a do. 78 Q l3 1.5 do. a do. 80 R l5 2.0 do. a do. 5 --l8 1.0 a 79 Developing solutions obtained by adding Compounds wherein R R R and R which can be the same or different, each represents a hydrogen atom, an alkyl group having from one to four carbon atoms, a phenyl group or nitrophenyl group, and wherein one of R R R or R may be a CONHR group in which R represents a hydrogen atom or an amino group,

said hydrazine is present in an amount ranging from 0.1g to 20.0g per liter of developing solution.

2. The developing composition of claim 1, wherein said composition contains formaldehyde-sodium bisulfite adduct.

3. The developing composition of claim 1, wherein said dihydroxy benzene-type developing agent is hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, or 2,5-dimethylhydroquinone.

' wherein R and R is a hydrogen atom or methyl group,

4. The developing composition of claim 3, wherein wherein R R R and R which can be the same or different, each represents a hydrogen atom, an alkyl group having from one to four carbon atoms, a phenyl group or nitrophenyl group, and wherein one of R,, R R or R may be a CONHR group in which R represents a hydrogen atom or an amino group,

said hydrazine being present in an amount of from 0.1g to 20.0g per liter of developing solution.

8. The method of claim 7, wherein said composition contains formaldehyde-sodium bisulfite adduct.

9. The method of claim 7, wherein said dihydroxy' benzene-type developing agent is hydroquinone, chlorohydroquinone, bror'nohydroquinone, isopropylhydroquionone, toluhydroquinone, methylhydroquinone,

2, 3-dichlorohydroquinone, or 2,5-dimethylhydroquinone.

10. The method of claim 9, wherein said dihydroxy benzene-type developing agent is hydroquinone.

11. The method of claim 7,-wherein said dihydroxy benzene-type developing agent is present at a level ranging from 5 to 50 g per liter of developing solution.

12. The method of claim 7, wherein R is a methyl group, an ethyl group or a CONT-l group, wherein R and R is a hydrogen atom or methyl group, and wherein R is a hydrogen atom. 

2. The developing composition of claim 1, wherein said composition contains formaldehyde-sodium bisulfite adduct.
 3. The developing composition of claim 1, wherein said dihydroxy benzene-type developing agent is hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, or 2,5-dimethylhydroquinone.
 4. The developing composition of claim 3, wherein said dihydroxy benzene-type developing agent is hydroquinone.
 5. The developing composition of claim 1, wherein said dihydroxy benzene-type developing agent is present at a level ranging from 5 to 50 g per liter of developing solution.
 6. The developing composition of claim 1, wherein R1 is a methyl group, an ethyl group or a CONH2 group, wherein R2 and R3 is a hydrogen atom or methyl group, and wherein R4 is a hydrogen atom.
 7. A method for forming photographic images for the graphic arts comprising exposing a high contract photographic element having a silver chloride content of not less than 50 mol percent and developing said exposed element in a developer composition comprising a dihydroxy benzene-type developing agent, a member selected from the group consisting of an aldehyde-alkali metal bisulfite adduct, a ketone-alkali metal bisulfite adduct, and a combination thereof and at least one hydrazine compound having the formula
 8. The method of claim 7, wherein said composition contains formaldehyde-sodium bisulfite adduct.
 9. The method of claim 7, wherein said dihydroxy benzene-type developing agent is hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquionone, toluhydroquinone, methylhydroquinone, 2, 3-dichlorohydroquinone, or 2,5-dimethylhydroquinone.
 10. The method of claim 9, wherein said dihydroxy benzene-type developing agent is hydroquinone.
 11. The method of claim 7, wherein said dihydroxy benzene-type developing agent is present at a level ranging from 5 to 50 g per liter of developing solution.
 12. The method of claim 7, wherein R1 is a methyl group, an ethyl group or a CONH2 group, wherein R2 and R3 is a hydrogen atom or methyl group, and wherein R4 is a hydrogen atom. 